A method to calculate the multiplet states of lanthanide impurities in solids is presented. This approach is based on a semi-empirical density functional method which includes corrections to account for the correlation and spin-orbit coupling of the 4f electrons. Specific multiplet states of the rare earth are produced by constraining the system. This approach is then used to investigate some of the properties of substitutional europium impurities in gallium nitride, reproducing the relative energy of two multiplets, and discussing a potential excitation mechanism for these centers.

Comparative studies have been carried out on the cathodoluminescence (CL) and photoluminescence (PL) properties of GaN implanted with Tm and GaN co-implanted with Tm and a low concentration of Er. Room temperature CL spectra were acquired in an electron probe microanalyser to investigate the rare earth emission. The room temperature CL intensity exhibits a strong dependence on the annealing temperature of the implanted samples. The results of CL temperature dependence are reported for blue emission (∼ 477 nm) which is due to intra 4f-shell electron transitions (1G4 → 3H6) associated with Tm3+ ions. The 477 nm blue CL emission is enhanced strongly as the annealing temperature increases up to 1200°C. Blue PL emission has also been observed from the sample annealed at 1200°C. To our knowledge, this is the first observation of blue PL emission from Tm implanted GaN samples. Intra-4f transitions from the 1D2 level (∼ 465 nm emission lines) of Tm3+ ions in GaN have been observed in GaN:Tm films at temperatures between 20–200 K. We will discuss the temperature dependent Tm3+ emission in both GaN:Tm,Er and GaN:Tm samples.